Azanol dyes



Patented Mar. 7, 1950 Alfred w. Anish, Vestal, and Lee 0, Hensley, Binghamtom N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware No Drawing. Application August 9, 1946, Serial No. 689,503

This invention relates to new dyes of the azanol type which are particularly useful for the preparation of photographic filters, anti-halation layers, and for sensitizing photographic silver-halide emulsions, and to a process of preparing the same. sensitizing dyes, comprising two heterocyclic nitrogenous nuclei linked by a chain of atoms including one or more nitrogen atoms, are known. These dyes are prepared by condensing a quaternary cyclammonium cyanine dye intermediate,

14 Claims. (01. 26 -240) containing an active group in the alpha or gamma position, with a diamine, such as, for example, hydrazine, ethylene diamine, p-phenylene diamine, and the like. These condensation prodnets are, for the most part, insoluble in aqueous solutions of inorganic bases and do not form metal salts with such bases. Moreover, theseproducts are incapable of forming heavy metal salts.

' We have discovered that by condensing a 5- or 6-membered keto heterocyclic compound, containing a reactive group, with an aliphatic, aromatic or heterocyclic diamine while heating in the presence of an alcohol as a solvent-diluent with or without a tertiary base, new dyes are obtained which are not only soluble in aqueous solutions of,

inorganic bases, but also form stable, heavy; metal salts, particularly silver salts.

usual processing baths. These properties not only make the dyes valuable as sensitizing dyes, but also as filter and anti-halation dyes for silverhalide emulsions.

Accordingly, therefore, it is an objectw f the present invention to provide a new class of azanol dyes.

A further object involves a method ofprepar ing such dyes.

Another object is to provide a photographic element comprising a silver-halide emulsion containing an azanol dye.

A still further object is to provide azanol dyes and heavy metal salts thereof which are added to photographic emulsions or coated thereon as an overcoating.

Other objects and advantages of this invention will become apparent by reference to the following specification in which its preferred details and embodiments are described.

The azanol dyes prepared according to the present invention are characterized by the following general formula: I

C-(OH=),,=NX-'N=(GH=),.-C\. 4 I i I .Q- e:

The silver salts are non-diiiusing and readily dischargeablein the wherein A represents the s toms necessary to complete a 5-membered or 6-membered heterocyclic nucleus, e. g., of a barbituric acid, a thio-barbituric acid, a rhodanine, an oxazoledione, a thiazolone, a pyrazolone, a hydantoin, a thiohydantoin, and the like, n represents a positive odd integer not greater than 3, and N-X-N is the radical of a primary diamine, said diamine being hydrazine, an aliphatic, aromatic, or heterocyclic diamine containing not more than 14 carbon atoms. For instance, when the primary diamine is aromati-c, the compounds have the following structure:

O-(-CH=),.=N-Ar-N=(OH=),.-C

, 2- -0R RO- wherein Ar represents an aromatic radical containing upto 12 carbon atoms.

' The process of preparing the above azanol dyes comprises heating, preferably under reflux conditions, with or without a tertiary base, an alcoholic solution of hydrazine, or an aliphatic, aromatic or heterocyclic diamine with a S-membered or 6- membered heterocyclic intermediate derived from abarbituric acid, a thio-barbituric acid, a rhodanine, a hydantoin, a thiohydantoin, an oxazoledione, a thiazolone, a pyrazolone, and the like, having a reactive acetanilido group linked to a carbon atom of a monoor polymethine chain of not more than 3 carbon atoms adjacent to a keto group of such intermediate.

, The diamines used in the preparation of the new dyes of the present invention, and having the general formula:

I Hm- X -NHZ wherein N-XN has the same significance as above, are the following:

Hydrazine Ethylenediamine o and p-Phenylenediamine 1.5j-naphthylenediamine 2:2'-, 2:4'-, and 4:4-diaminostilbene 4,4-diamine-3,3-dich1orophenylmethane 4,4'-diamino-benzophenone 4,4'-diamino-3,3'-dimethoxydiphenylmethane p-p'-Diamino-diphenylmethane 2,6-diamino-pyridine 2,5-diamino-thiodiazole 2,4-diamino-quinoline 2,4-diamin0-6-thio-3,5-thiabiazine a 'The 5-membered heterocyclic intermediates derived from a rhodanine, a thiazolone, a hydantoin, an oxazoledione and a pyrazolone are de- (0.005 mol+10%) of p-phenylenediamine, 125 cc. scribed in United States Patent 2,186,608 and repof isopropyl alcohol and 0.5 cc. of triethylamine resented by the general formula: was refluxed on a steam bath for about 1 hour,

00333 A during which time the dye separated from the I a hot alcohol. The mixture was filtered while hot, N and the filter residue boiled out twice with 100 cc. wherem A and v the same sigmficance portions of methanol. The dye was further puriabove. As illustrative of compounds represented by dissolving it in N/i caustic solution, by this general formula reference is made to: Bring the Solution f ll and precipitating 4-( acetanilidoallylidene) 1 (2) benzothawith dilute acetic acid.

zolyl-3-methyl-5-pyrazolone The dye sensitized a silver chlorobromide emul- 4-acetanilidomethylene-3-methyl 1 pheny1-- 5 'sion to 590 m with a maximum at 545 mu.

pyrazolone EXAMPLE 4-(v-acetanilidoallylidene) 3-methyl-l-phenyln azolone S-C'-OH=N-ON=CHC-S 4 acetanilidomethylene 3 methyl 1 (2) Ii II I pyridyl-5-pyraz0lone i J =8 3-acetani1idomethylene-5 methyl thiophen 2- N one (JaHt lHfi S-acetanilidomethylene-3-allylrhodanine 5-acetanilidopropanylidene-3-allylrhodanine 5-acetanilidomethylene-3-phenylrhodanine 5-acetani1idomethylene-3-ethylrhodanine 5-acetanilidomethylene 3-ethyl-2-thio-2,4(3,5)

In a manner similar to that used in the preparation of the dye described in Example I, 0.4 gram of benzidine was reacted with 1.2 grams of 5 a'cetanilidomethylene-3-allylrhodanine. This dye sensitized a silver chlorobromide emulsion to oxazoledione 5-(Y-acetanilidoallylidene) 2 diphenylamino- 570 wlth maxlmum 520 4 (5) -thiazolone EXAMPLE IlI 5-('y-acetanilidoallylidene) 3 ethyl 2 thio- 2,4(3,5) -oxazoledione s fi O O 'fi 5-(y-acetanilidoallylidene) -3 ethyl 1 phenyl- Si HOO =S 2-thiohydantoin 5- (5 acetanilido A pentadienylidene) 3 ethylrhodanine 5 i 5-(*y-acetanilidoallylidene) 2,4,6 triketohexa- Y es gram of P qhydropyrimjdjne methane with 1.2-grams of 5-acetan111domethyl- 5-('y-acetanilidoallylidene) 2 thio 4,6-diketoene-3-ellylrhodanine in isopropyl alcohol, accordhexahydropyrimidine, and t m ing to the method of Example I, a yellow dye was obtained. This dye sensitized a silver chloro- As solvent-diluents employed in the preparation of the new dyes of the present invention, the ggg fig emulslon to 530 wlth a maxlmum at following alcohols may be employed: methyl, EXQHP ethyl, propyl, isopropyl, butyl, benzyl, furfuryl LEW alcohol and the like. Triethylamine, tributyl- HC--OCH=N-ON=CHC-OH amine, and the like are representative of the ter- L ii L tiary bases which we may use.

When 1 mol of a diamine, of the type men-- S S tioned above,iscondensed with 1mo10fa5-mem- -While following the procedure of Example I, bered or 6-membered heterocyclic intermediate 1.0 a Of D-p y e d a and grams in the presence of an alcohol, with or without a of' 3-acetanilidomethylene-5 methyl-thiophen-2- tertiary base as a catalyst, a'reaction occurs which one were reacted in 150 cc. of isopropyl alcohol maybe formulistically written as follows: in the presence of 1 cc. of triethylamine. The

-011 H0- 1 The following examples describe in detail the resulting dye sensitized a silver chl'orobromide methods for accomplishing the above objects, but emulsion to 530 m with a maximum at 510 m it is to be understood that they are inserted merely for the purpose of illustration and are not EXAMPLE v to be construed as limitative. Hfi-'-0-c11=NOON=cH-c-cn EXAIVIPIE I g Hid-C t-0H no-t'i c -oin in Z E' C fiT While :following the procedure of' Example I, H 1 j 7.0 0.2 'gr'am cf benzidine and 1.0 gram of B-acet- I H anilidomethylene-B-methylthiophen-Z-one were 1 I i I reacted in 15 cc. of isopropyl alcohol in the presence oi 'several drops of triethylamine. The re- .'A:,,=.mixtureof. '3-.-2 :grams (0.01 mol) of Y5- sulting dye sensitized a silver chlorobromide acetanilidomethylene-3-a11ylrhodanine, 0.6 gram 7 emulsion to 520 m with a maximum at 480 my.

55?. EXAMPLE VI EXAMPLE VII N N 3 H5 an. Three grams of 4-acetanilidomethylene-1- phenyl-3-methyl-5-pyrazolone and 0.5 gram of p-phenylenediamine were reacted together in 70 cc. of isopropyl alcohol in the presence of a few drops of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 520 m with a maximum at 470 mp.

EXAMPLE VIII 1.0 gram of p-phenylenediamine and 4.0 grams of 5-acetanilidomethylene-3-phenyl-2,4 thiazoledione were reacted in 150 cc. of isopropyl alcohol in the presence of 1 cc. of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 530 m l, with a maximum at 510 m 1.0 gram of p-phenylenediamine and 4.0 grams of 5-acetanilidomethylene-3-phenyl-2,4-thiazoledione were reacted in 150 cc. of isopropyl alco- 6 hol in the presence of 1 cc. of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 530 ml, with a maximum at 510 m lHi I dirt Six grams each of 5-acetanilidomethylene-3 allylrhodanlne and ethylene diamine were dissolved in 250 cc. of isopropyl alcohol, and the mixture refluxed for 1 hour. During this time, a

5 yellow solid separated. After cooling, thereaction mixture was filtered oil and the dye recrystallized from methanol. The dye sensitized a silver chlorobromide emulsion to 480 m l, with a maximum at 440 m A mixture of 6.0 grams of 5-acetanilidomethylene-3-allylrhodanine, 0.5 gram of an 85% aqueous solution of hydrazine hydrate, cc. of isopropyl alcohol, and one drop of triethylamine were refluxed for 1 hour. The pale yellow precipitate, which formed, was filtered ofi and boiled out with several portions of methanol. The insoluble portion was recrystallized from methanol. The dye sensitized a silver chlorobromide emul- 25 sion to 470 m with a maximum at 430 my.

EXAMPLE XII A mixture of 4.4 grams of 5-(y-acetanilidoallylidene) 2 diphenylamino 3 ethyl 4(5) thiazolone, 1.0 gram of p-phenylenediamine, 125 cc. of isopropyl alcohol and 0.5 cc. of triethylamine were refluxed on a steam bath for about 1 hour, during which time the dye separated from the hot alcohol. The mixture was filtered while hot and the filter residue boiled out twice with 100 cc. portions of methanol. The dye was further purified by dissolving it in N/l-caustic solution, filtering the solution carefully and preeipitating with dilute acetic acid.

EXAMPLE XIII 3.0 grams of 5-(aoetanilidomethylene) -3-ethyl- 2-thio-2,4(3,5) -oxazoledione, and 1.1 grams of 2,6-diamino-pyridine were mixed with 20 cc. of isopropyl alcohol containing 1 cc. of triethylamine. The mixture was boiled, under reflux, for

0 1 hours, cooled and then diluted with 15 cc. of water. The dye which separated was boiled out twice with ethyl alcohol and then dried.

EXAMPLE XIV HO-C Three grams of 5-('y-acetanilidoallylidene)-3- ethyl-1-phenyl-2-thiohydantoin and 1.0 gram of p-phenylenediamine were dissolved in '70 cc. of isopropyl alcohol, containing about 1 cc. of triethylamine, and the mixture heated under re- 76 flux for about 1 hour. After cooling to room temperature, the mixture was filtered: and'the residue boiled out twice with 100 cc. of methanol.

A mixture of 3.0 grams of ('y-acetanilidoallylidene) 2,4,6 triketohexahydropyrimidine, 0.5 gram of an 85% aqueous solution of hydrazine hydrate and 50 cc. of isopropyl alcohol, containing 1 drop of triethylamine, were refluxed for 1 hour. After cooling to room temperature, the solid product which separated out was segregated from the supernatant liquid by decantation. The solid was boiled out twice with 95% methyl alcohol and then dried.

EXAMPLE XVI A mixture of 3.1 grams of 5-(y-acetanilidoallylidine) 2-thio-4,6-diketohexahydropyrimidine, 1.0 gram of p-phenylenediamine and 50 cc. of isopropyl alcohol and 1 drop of triethylamine were refluxed for 1 hour. The solid' which precipitated was filtered off and boiled with several portions of methanol.

In the preparation of emulsions containing these azanol dyes, the dye may be dissolved in methyl or ethyl alcohol, and a volume of this solution containing from 5 to 50 milligrams added to a liter of emulsion.

It will be understood that wherein the claims appended hereto the term filter layer is used, that such is intended to include anti-halation layers. While in general practice it may not be necessary to add the dye in amounts larger than those above given, generally, for satisfactory results, amounts usually ranging from 5 to 25 milligrams are sulficient to obtain the maximum sensitizing efiect. However, we do not wish to limit our invention to the quantities just indicated as the most suitable amount will be found, in each case, by a few comparative experiments. The dyes may be added to the. emulsion in the form of solutions. Suitable solvents as indicated in the examples are the alcohols, for instance, methyl or ethyl alcohol which may be anhydrous or diluted with a small volume of water. In actual practice, the dyes are applied to the emulsion during any stage of its production, however, they are preferably added to thefinished emulsion before being cast.

The above examples are illustrative, only, and should not be construed as limiting the invention, since it will be apparent to those skilled in the art that the dyes of the present invention may be incorporated into photographic emulsions by methods other than those described herein.

The dyes of this invention are further characterized by their ability to form insoluble heavy metal salts, e. g., silver, lead and mercury salts, due to the presence of a salt-forming hydroxyl group. Thus, for example in the presence of silver ions, insoluble silver salts are formed. These silver salts, moreover, are soluble in photographic processing baths, such as sodium thiosulfate. Accordingly, the dyes of this invention are readily applicable as non-difiusing photographic filter and anti-halation dyes in photographic materials in the form of their silver salts. The dyes may be incorporated directly into the photographic. emulsion, or applied in a known manner underneath. the emulsion layer, intermediate layer between the support and emulsion, as a backing layer on the rear surface of the emulsion support, or as an interlayer between the two emulsion layers.

The following examples illustrate the use of thedyes of this invention in the form of silver salts as filter and anti-halation agents.

EXAMPLE XVII A photographic filter layer was prepared by mixing the following ingredients to form a colored silver salt dispersion in gelatin:

. Solution A Compound of Example I grams 2.? Water cc Sodium carbonate (anhydrous) grams 2.1 Gelatin (10% solution) cc 25 Solution B Water cc 100 Silver nitrate grams 1.7

Solution 0 Gelatin (10% solution) cc 100 Solution B was added to Solution A with rapid stirring. After several minutes, Solution C was added. The silver of the silver nitrate formed a silver salt with the hydroxy group of the dye in the gelatin solution. The final gelatin suspension thus obtained was then coated on a photographic film in the customary manner to serve as a yellow filter layer for blue light absorption. The silver salt of the dye is non-diffusing.

The amount. of silver salt used according to the present invention will vary somewhat, depending upon the color desired. In general, an amount more or less than that given in Example XVII may be used for satisfactory results.

For the production of anti-halation coatings, the silver salts of the azanol dyes of the present invention ar incorporated into gelatin, treated with silver nitrate, and the dispersions thus obtained are cast in a known manner as coatings underneath the emulsion layer, intermediate layer, between the support and the emulsion or as a backing layer onthe rear surface of the emulsion support, or as a support on the emulsion, when th material is intended to be exposed through the support.

EXAMPLE XVIII A photographic anti-halation layer was prepared by mixing the following ingredients to form a colored silver salt dispersion in gelatin:

Solution B was added to Solution A with rapid stirring. After several minutes, Solution C was added. The final gelatin suspension of the silver salt thus obtained was coated on a support 16 in the customary mann r as an anti-halation complete a memberselected from the class conlayer. sisting of a E-membered and G-membered heter- The filter and anti-halo" coatings prepared as y i n s st m, R s a m mber s lect d from described above have been found to have parthe class consisting of hy gen and a heavy ticularly good filter and anti-halant properties metal, 1! represents a po Odd integer o from and t have no efiect on th normal keeping 1 to 3, and'N--XN is a radical of an amine conproperties of the light-sensitive layer. taming tWO P a y o group of not more While 'thejpresent invention has been described than'Il carbon atoms and selected from the class in considerable detail with reference to certain consisting of hydrazine, aliphatic and aromatic preferred procedures, materials and uses, it isun- Primary diamines, d 2-6-diamin0 pyridine, derstood that the new class of azanol dyes and diamino thiodiazole, 2.4-diamino quinoline, and their use as sensitizing, filter and anti-halation 0 -thio3.5-thi0diazine.

dyes is not limited thereto, and that numerous 2415251101 dyes a ac eri ed by the :following variations and modifications described in the general formula! Y foregoing specification may be made as, for exb NQM N=( CH=)FO ample, the dyes which contain aketo-heterocyclic 2 5 nucleus, e. g., oxazoledione, hydantoin, and rhodanine nucleus, as illustrated in Examples 1-3, RO-O 8-10, and 13-15 inclusive, may be further treated wherein A represents the atoms necessary to comwith a quaternizing compound such as methyl plete a member selected from the class consistiodide. The quaternized compound is then coning of a 5-membered and G-membered heterodensed under reflux conditions with a cyclamcyclic ring system, B, is a member selected from monium base or salt usual in cyanine dyes, such the class consisting of hydrogen and a heavy as N-methyl-2-methylbenzthiazole, having a remetal, 11, represents a positive odd integer of from active methyl group in the alpha-position to the 1 to 3, and Ar represents an aromatic radical connitrogen atom in the presence of a condensing taining up to 12 nuclear carbon atoms.

agent such as pyridine, quinoline and the like. 3. Ozanol dyes as defined in claim 2, wherein In the first reaction (alkylation) the azanol dye Ar is phenyl.

is modified to the extent that the nitrogen atom 4. Azanol dyes characterized by the following in the 3-position of the oxazoledione, hydantoin general formula:

or rhodanine ring is quaternized and the sulfur C OH=)H=N N=( OH=)R C atom in the 2-position is converted to a thioether group. In the second reaction (condensation),

the alkylated azanol dye is condensed with a cycl- Ro-o ammonium base or salt whereby new compounds, wherein A represents the atoms necessary to comwhich are also useful as sensitizers, filter and plete a member selected from the class consistanti-h-alation agents, having the following gening of a 5-membered and G-membered heteroeral formulae, are obtained: cyclic ring system, R is a member selected from wherein R, =N-X--N=, and n have the same the class consisting of hydrogen and a heavy values as above. R1 represents an alkyl, alkylene metal, and n represents a positive odd integer of or aryl radical, R2 represents alkyl, P and Q, from 1 to 3.

which may be the same or different, represent 5. Azanol dyes and the hydroxy heavy metal the atoms necessary to complete a heterocyclic salt thereof corresponding to the formula: ring system of the type usual in cyanine dyes, e. g., indolenines, lepidines, oxazoles, oxazolines, f'fi- *O selenazoles, selenazolines, pyridine, quinoline, s=o 0-03 EEO- (8:5 thiazoles, thiazolines, diazoles and quinazolines and the corresponding polycyclic compounds, A

such as benzthiazoles, benzselenazoles, naphthothiazoles, naphthoselenazoles, diazines and the Azanol dyes and the hydroxy heavy metal like Y represents 0, S, or N C6H5, and Z repre salt thereof corresponding to the formula: sents a dye-precipitating acid radical of the type usual in cyanine dyes. All such modifications Z G D 'Z and variations are within the scope of this inven- HO- o=s tion as defined by the appended claims. N

We claim: 6 a 1. Azanol dyes characterized by the following 7. Azanol dyes and the hydroxy heavy metal general formula: 7 salt thereof corresponding to the formula:

o -on=),.=N-x-N= -oH=),.-o S=( J I OH HO-O o=s 0R Ro-o' wherein A represents the atoms necessary to 5,

25300541 1 11 8. The :compound "as defined 'inrclaim 5, wherein the hydroxy heavy metal :salt is silver.

9. The compound as defined in nlaimfi, wherein the hydroxy heavy metal saltis silver.

10. The compound as "defined in claim 7, 5 wherein the hydroxy heavy metal salt is silver.

11. The compound as defined in claim 1, Number wherein R of the OR group is replaced by silver.

12. The compound as defined in claim 2,

wherein R of the oRigroup is replaced by silver. 10 253073-49 13. The compound as defined in claim 3, 2,340,882 wherein R of the 012. group is replaced by 'silver.

14. The compound as defined :in claim 4, wherein R of the OR group is replaced-by vsilver.

ALFRED W. ANISH. u LEE C. HENSLEY.

REFERENCES CITED The following references are of record in the file of this'pabent:

UNITED STATES PATENTS Name Date Keyes Jan. 9, 1940 Gaspar Mar. 3, 1942 Kendall Jan. 5, 1943 Kendall Feb. 8, 1944 Gaspar Mar. 28, 1944 Kendall Jan. "30, 1945 

1. AZANOL DYES CHARACTERIZED BY THE FOLLOWING GENERAL FORMULA: 